CN107579214B - Method for preparing silicon-carbon composite material by taking silicate glass as raw material, product and application thereof - Google Patents
Method for preparing silicon-carbon composite material by taking silicate glass as raw material, product and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a silicon-carbon composite material by taking silicate glass as a raw material, a product and an application thereof, wherein the method comprises the following steps: and carrying out wet ball milling on the glass powder and the carbon material to obtain a uniform mixed product of the glass and the carbon material, uniformly mixing the uniform mixed product with magnesium powder and molten salt, pressing the mixture into ingots to carry out magnesium thermal reaction, and carrying out acid washing treatment on the reaction product to obtain the carbon and silicon composite material with different structures. The method has simple and easy steps and wide raw material sources, and most importantly, the mixture is made into ingots and then subjected to magnesium thermal reaction, so that the tap density of the silicon-carbon negative electrode material is greatly increased, the volume specific capacity of the negative electrode material is improved, the electronic conductivity of the silicon-carbon composite material formed by compounding the silicon-carbon composite material with a graphitized carbon material is also effectively improved, and the compatibility of the silicon-based material and an electrolyte is improved, so that the cycle performance and the rate capability of the material are improved, and the method can be applied to the lithium ion battery negative electrode material with high power density and high energy density.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a method for preparing a silicon-carbon composite material by taking silicate glass as a raw material, a product and application thereof.
Background
The energy crisis and environmental problems of the current society are increasingly prominent, and the storage of novel clean energy and energy has become a hotspot of research of people. The lithium ion battery has the characteristics of high energy density, high power density, long service life, environmental friendliness and the like, and has wide application prospects in the fields of electric automobiles, large-scale energy storage equipment, distributed mobile power supplies and the like. However, the specific mass capacity and energy density of the lithium ion battery need to be further improved to meet the requirements of miniaturization of portable electronic products and application thereof in aerospace, military, power grid peak regulation and electric automobiles. Among many negative electrode materials for lithium ion batteries, silicon is considered as a negative electrode material having great potential for the next generation of lithium ion batteries due to its exceptionally high specific capacity, abundant reserves in the earth crust, and advantages of the developed industrial infrastructure of manufacturing industry. Therefore, the development of lithium ion battery materials with high specific capacity and high specific energy has become a very important research topic in current work. However, the scaling of silicon anode materials should solve two key problems: particle pulverization, falling and electrochemical performance failure caused by volume expansion and contraction accompanying with the silicon particles during lithium extraction; continued growth of the solid electrolyte layer (SEI) on the surface of the silicon particles is an irreversible depletion of the electrolyte and lithium source from the positive electrode. The preparation of silicon-carbon composite materials is one of the effective approaches to solve the above problems.
At present, the silicon-carbon composite material mainly comprises a coating type and an embedding type. The coating structure is to coat a carbon layer on the surface of the active material silicon, so that the volume effect of the silicon is relieved, and the conductivity of the silicon is enhanced. The coating structure may be classified into a core-shell type, a yolk-shell type, and a porous type according to the coating structure and the morphology of the silicon particles. The coating structure is to coat a carbon layer on the surface of the active material silicon, so that the volume effect of the silicon is relieved, and the conductivity of the silicon is enhanced. The coating structure may be classified into a core-shell type, a yolk-shell type, and a porous type according to the coating structure and the morphology of the silicon particles. However, the existing methods for preparing the silicon-carbon composite material have the disadvantages of harsh conditions, high cost, complex steps, serious pollution, involvement of a plurality of toxic substances and great harm to people. For example, in the "preparation method of silicon-carbon anode material" (CN104103821A), a catalyst is first placed in a chemical vapor deposition reaction chamber; heating the chemical vapor deposition reaction chamber, introducing a reaction gas source and a carrier gas into the chemical vapor deposition reaction chamber, and making Si-SiOx generated in the chemical vapor deposition reaction process pass through a dynamically rotating carbon matrix subjected to carboxylation treatment to prepare a precursor of the silicon-carbon negative electrode material. The process has high risk coefficient, large operation difficulty coefficient and high cost, and is not suitable for large-scale production. For another example, in "a method for preparing a polymer silicon carbon negative electrode material" (CN106356520A), nano silicon and graphite are compounded, and then carbonized at high temperature under the action of various dispersants and binders, and a layer of amorphous carbon is coated on the surface of the nano silicon and graphite, and then spray-dried to obtain the polymer silicon carbon composite negative electrode material, but the silicon carbon negative electrode material prepared by the method contains a heterogeneous phase, which affects the performance of the negative electrode material. In addition, the nano silicon carbon is coated by using PAN, for example, the document "A < energy > for enabling a large quantity of low Si @ CnanOStrured anode for lithium ion batteries" (RSC adv.2015,5, 6782-6789), the silicon carbon composite material prepared by the method has low volume energy density due to the core-shell structure, and the used raw materials are relatively expensive and cannot be widely applied in a large scale.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a method for preparing a silicon-carbon composite material by taking silicate glass as a raw material, a product and application thereof, the method aims to carry out carbonization treatment after uniformly mixing waste silicate-based glass powder and a carbon material through wet ball milling, then mixing with magnesium powder and fused salt, compacting into ingots, carrying out magnesium thermal reaction to obtain the silicon-carbon composite material, the preparation method is simple, the process is safe, the cost is low, the prepared silicon-carbon composite material has high tap density and compacted density, has good performance when being used as a lithium ion battery cathode material, thereby solving the problems of harsh preparation conditions, high cost, complex steps, serious pollution and the like of the silicon-carbon cathode material in the prior art, meanwhile, the prepared silicon-carbon cathode material has low volume energy density and mass energy density and cannot meet the application requirements of the battery cathode material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a silicon-carbon composite material, comprising the steps of:
(1) mixing silicate glass powder and a carbon material, performing wet ball milling, performing solid-liquid separation, and drying to obtain a uniformly mixed mixture of the silicate glass powder and the carbon material;
(2) carbonizing the mixture of the silicate glass powder and the carbon material obtained in the step (1), and grinding the mixture after annealing to obtain a mixture of the silicate glass powder and the carbon material after carbonization;
(3) mixing the mixture of the silicate glass powder and the carbon material subjected to carbonization treatment in the step (2), magnesium powder and molten salt, compacting into ingots, and then carrying out a magnesiothermic reduction reaction in an inert atmosphere; and carrying out acid washing treatment on the reaction product to obtain the silicon-carbon composite material.
Preferably, the particle size of the silicate glass powder in the step (1) is 1-4 microns.
Preferably, the carbon material is a carbon-containing organic composite or a one-dimensional carbon material, the carbon-containing organic composite including one or more of pitch, petroleum coke, coal tar, phenolic resin, graphene, and biomass carbon; the one-dimensional carbon material comprises one or more of carbon fiber, bacterial cellulose and carbon nanotubes.
Preferably, the mass ratio of the silicate glass powder to the carbon material in the step (1) is 10: 2-5.
Preferably, the wet ball milling time in the step (1) is 6-12 hours, and the adopted solvent is n-amyl alcohol.
Preferably, the carbonization treatment in step (2) comprises the following specific steps: heating to 400-550 ℃ at a heating rate of 1-5 ℃/min under an argon environment, preserving heat for 1-3 h, and then heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 2-4 h.
Preferably, before the carbonization treatment in step (2), the method further comprises the substeps of: compacting the mixture of silicate glass powder and carbon material into an ingot.
Preferably, the pressure range for compacting the mixture of silicate glass powder and carbon material into ingots is 0.5-2 MPa.
Preferably, the mass ratio of the mixture of the silicate glass powder and the carbon material after the carbonization treatment in the step (3) to the magnesium powder and the molten salt is 1: 0.5-0.6: 3 to 5.
Preferably, said compacting into ingots is effected by a press, hydraulic press or cold press.
Preferably, the pressure range adopted by the compaction into ingots in the step (3) is 1-5 MPa.
Preferably, the molten salt of step (3) comprises one or more of magnesium chloride, sodium chloride and potassium chloride.
Preferably, the dissolved salt is a mixture of sodium chloride and potassium chloride in equal mass proportion.
Preferably, the magnesiothermic reduction reaction conditions of step (3) are: heating to 600-800 ℃ at a heating rate of 2-5 ℃/min in an argon atmosphere, and preserving heat for 3-6 h.
According to another aspect of the invention, a silicon-carbon composite material is provided, and the silicon-carbon composite material is prepared according to the preparation method.
Preferably, the tap density of the composite material is 1.03-1.27 g/cm3The compaction density is 1.46-1.63 g/cm3The specific surface area is 100 to 150m2g-1。
Preferably, the content of silicon in the composite material is 80-90 wt%, and the balance is carbon.
According to another aspect of the invention, the application of the silicon-carbon composite material is provided, and the silicon-carbon composite material is applied to a lithium ion battery negative electrode material.
In general, the above technical solutions contemplated by the present invention can achieve the following advantageous effects compared to the prior art.
(1) The preparation method of the silicon-carbon composite material sequentially adopts wet ball milling, carbonization treatment and hydraulic technology, silicate-based glass and a carbon material are uniformly mixed through the wet ball milling, the mixture is hydraulically pressed into ingots for carbonization treatment, the ingots are mixed with magnesium powder and molten salt after annealing, then the ingots are pressed, then magnesium thermal reaction is carried out, and finally the reaction product is acid-washed to obtain the silicon-carbon composite material. Wherein, the wet ball milling ensures that the silicate glass powder is uniformly mixed with the carbon-containing material, and lays a foundation for the uniform distribution of the final silicon and carbon in the composite material; the purpose of carbonization is to enhance the crystallinity of the carbon material and enhance the conductivity of the silicon-carbon composite material on the basis of uniform mixing of the carbon material and the silicon-carbon composite material; the compacting ingot forming technology is characterized in that reactants and molten salt are mixed and compacted together under the action of mechanical force, a compact porous silicon ingot with different structures and carbon composites is obtained after thermal reaction, the tap density and the compacted density of the porous silicon ingot are not inferior to the level of the current commercial graphite, and the volume density of the prepared composite material is greatly improved.
(2) The silicon-carbon composite material provided by the invention can obtain silicon-carbon composite materials with different structures according to different types of initial carbon materials. The composite material has high tap density and compacted density, high specific mass capacity and specific volume capacity, limited electrode expansion and excellent cycling stability, and is an ideal material for a lithium ion battery cathode.
(3) The waste silicate glass and the common carbon material are used as raw materials to prepare the silicon-carbon composite material, and the waste silicate glass and the carbon material have low cost and rich content and are cheap and high-quality raw materials for producing the silicon-carbon cathode of the lithium ion battery.
(4) In the preparation process, halides such as magnesium chloride, potassium chloride, sodium chloride and the like are used as molten salts, and the melting points of the molten salts are also 600-800 ℃, so that on one hand, the stable reaction environment is ensured, and the molten salts are used as heat absorbing agents to prevent grains from growing too fast and refining the grains, can prevent the agglomeration and sintering of products, can prevent byproducts from generating and improve the product purity, and ensure that the whole reaction is more suitable to be carried out, the reaction is more sufficient and the whole reaction is safer.
(5) The silicate glass is in a molten state at 600-800 ℃, the temperature is also in a reaction temperature range, the magnesium powder is also in a liquid state, and the liquid-liquid magnesium thermal reaction is superior to other solid-liquid magnesium thermal reactions, so that the magnesium thermal reaction is carried out at 680 ℃, the reaction can be fully carried out, and a uniformly compounded amorphous carbon-coated porous silicon structure is obtained.
(6) The invention designs and develops a simpler and greener synthesis method to prepare the porous silicon-carbon composite which has high reversible capacity and excellent cycle performance when used as the lithium ion battery cathode material, and the method for preparing the high-performance silicon-carbon cathode material, which has low cost, easy operation and large-scale production, is beneficial to the development of the next generation of lithium ion batteries.
Drawings
FIG. 1 is a scanning electron microscope image of a porous silicon/amorphous carbon composite material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the porous silicon/amorphous carbon composite material prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the porous silicon/amorphous carbon composite prepared in example 1 of the present invention;
FIG. 4 is a graph of electrochemical cycling performance of the porous silicon/amorphous carbon composite prepared in example 1 of the present invention;
fig. 5 is an adsorption and desorption curve and a pore size distribution curve of the porous silicon/amorphous carbon composite material prepared in example 1 of the present invention;
FIG. 6 is a thermogravimetric plot of the porous silicon/amorphous carbon composite prepared in example 1 of the present invention;
FIG. 7 is a scanning electron microscope image of a porous silicon/amorphous carbon composite material prepared in example 3 of the present invention;
fig. 8 is a scanning electron microscope image of the porous silicon/carbon nanotube composite material prepared in example 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the silicon-carbon composite material provided by the invention comprises the following steps:
(1) and mixing the silicate glass powder and the carbon material, performing wet ball milling, filtering, and drying to obtain a mixture of the silicate glass powder and different carbon materials which are uniformly mixed.
In the present invention, the particle size of the silicate glass powder is preferably in the range of 1 to 4 μm. The method for obtaining the silicate glass powder comprises the following steps: washing and drying the glass by deionized water, reducing the particle size of the glass by a mechanical ball milling method, and screening out glass powder with the particle size meeting the requirement by a 1000-mesh sieve. The silicate glass is sodium silicate glass or calcium silicate glass. The carbon material can be a carbon-containing organic compound or a one-dimensional carbon material, wherein the carbon-containing organic compound comprises one or more of asphalt, petroleum coke, coal tar, graphene, phenolic resin and biomass carbon; the one-dimensional carbon material includes bacterial cellulose, carbon fiber or carbon nanotube. The mass ratio of the silicate glass powder to the carbon material is 10: 2-5; the wet ball milling time is 6-12 hours, and the adopted solvent is ethanol or n-amyl alcohol, preferably n-amyl alcohol. Because n-pentanol can make the surface of the particles more easily carry hydroxyl functional groups and better combine with carbon materials.
(2) And (2) compacting the mixture of the silicate glass powder and the carbon material obtained in the step (1) into an ingot for carbonization, and grinding the ingot of the mixture after annealing to obtain the carbonized silicate glass powder and carbon composites with different structures.
The carbonization treatment comprises the following specific steps: heating to 400-550 ℃ at a heating rate of 1-5 ℃/min under an argon environment, preserving heat for 1-3 h, and then heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 2-4 h. The carbonization treatment has the function of ensuring that the carbon-containing material has good crystallinity at high temperature, enhancing the conductivity of the carbon material and further enhancing the conductivity of the silicon-carbon composite material.
(3) Mixing the carbonized silicate glass powder obtained in the step (2) with the compound of carbon with different structures, magnesium powder and molten salt, compacting into ingots, and then carrying out a magnesiothermic reduction reaction in an inert atmosphere; and carrying out acid washing treatment on the reaction product to obtain the silicon-carbon composite material.
The mass ratio of the carbonized silicate glass powder to the compound of carbon with different structures, magnesium powder and molten salt is 1: 0.5-0.6: 3 to 5. The molten salt comprises one or more of magnesium chloride, sodium chloride and potassium chloride, preferably an equal proportion mixture of sodium chloride and potassium chloride. And (3) compacting into ingots, namely maintaining the pressure for a certain time, such as 1-20 seconds, under a certain pressure, so that the materials are compacted into ingots, and the compaction can be realized by a hydraulic machine, a press machine, a cold extruder or other pressure equipment. According to the invention, the composite material obtained finally is greatly improved in tap density and compacted density by adopting twice hydraulic pressing into ingots, and the pressure range adopted by the hydraulic pressing into ingots before the carbonization treatment in the step (2) can be a little smaller, such as 0.5-2 MPa; and (4) adopting a pressure range of 1-5 MPa for pressing into ingots in the step (3). Under the pressure range of 1-5 MPa, the effect of ingots below or beyond the range is not ideal, or complete columnar ingots cannot be obtained, or integral collapse is caused, reactants and molten salt are mixed and compacted together, and the compact carbon porous silicon ingots with different structures are obtained after thermal reaction, wherein the tap density and the compacted density are not inferior to the level of the current commercial graphite. On the other hand, the pressure also directly influences the specific surface area of the finally prepared silicon-carbon composite material, the pore volume in the composite material is reduced along with the increase of the pressure, the specific surface area of the composite material obtained in the pressure range is not too high or too low, and the composite material can meet the requirement of the negative electrode material on the specific surface area when used for the negative electrode material of the lithium ion battery.
The magnesiothermic reduction reaction conditions are as follows: heating to 600-800 ℃ at a heating rate of 2-5 ℃/min in an argon atmosphere, and preserving heat for 3-6 h. The temperature of the magnesium thermal reaction is preferably 680 ℃, so that the reactants react in a molten state and have larger volume density after cooling and solidification.
The pickling step specifically comprises: and cleaning for 8-12 h in 0.5mol/L hydrochloric acid under the condition of stirring, then cleaning in 0.5mol/L hydrofluoric acid, and drying to obtain the carbon porous silicon composite product with different structures.
When a carbon-containing organic compound is used as a carbon material, the preparation method can be used for obtaining a silicon-carbon composite material coated by amorphous carbon, the composite material comprises porous silicon which is three-dimensionally communicated and amorphous carbon, wherein the amorphous carbon is coated on the surface of the porous silicon, the porous silicon is ant nest-shaped, the particle size of the porous silicon is 1-5 micrometers, the thickness of the amorphous carbon is 10-20 nanometers, the amorphous carbon is coated on the surface of the porous silicon, the size of a macroporous structure of the composite material is 100-200 nanometers, and the size of a mesoporous structure is10 to 20 nm. The tap density of the composite material is 1.03-1.17 g/cm3The compaction density is 1.56-1.63 g/cm3The specific surface area is 120-150 m2g-1The composite material comprises 80-90 wt% of silicon and the balance of carbon.
When carbon fibers or carbon nanotubes are used as carbon materials, the preparation method can be used for obtaining the silicon-carbon composite material with a network structure formed by inlaying and interweaving one-dimensional carbon nanowires or nanotubes and silicon, the composite material comprises porous silicon and carbon nanotubes or carbon nanofibers, the network structure formed by interweaving the carbon nanotubes or the carbon nanofibers is embedded into silicon particles, the particles are connected together and are wrapped and interweaved, and the carbon fibers or the carbon nanotubes have the length of 10-20 micrometers and the diameter of 10-20 nanometers. The tap density of the composite material is 1.13-1.27 g/cm3The compaction density is 1.46-1.60 g/cm3The specific surface area is 100 to 120m2g-1The composite material comprises 85-92 wt% of silicon and the balance of carbon.
The invention actually discloses a method for preparing a silicon-carbon negative electrode material by taking silicate-based glass as a raw material, which comprises the following steps: grinding silicate-based glass by mechanical ball milling, then using n-amyl alcohol as a solvent for glass powder and a carbon material according to a certain proportion, filtering and drying after wet ball milling to obtain a uniform mixed product of the glass powder and the carbon material, then carrying out hydraulic pressing on the obtained sample to obtain an ingot, carrying out carbonization treatment at a certain temperature under an argon environment, carrying out hydraulic pressing on the annealed sample after grinding and uniformly mixing magnesium powder and molten salt according to a certain proportion to obtain the ingot, and reacting under inert gas (M)xSiO3+2Mg＝2MgO+Si+MxO, M ═ Na, Ca, Al), and then the reaction product was subjected to acid washing treatment to obtain silicon-carbon composites of different structures. The method has the advantages of simple and easy steps, wide raw material source and low cost, and most importantly, the mixture is made into ingots through a simple hydraulic process and then subjected to magnesium thermal reaction, so that the tap density of the silicon-carbon negative electrode material is greatly increased, the volume specific capacity of the negative electrode material is improved, and the obtained porous silicon junction with the three-dimensional cross-linked structureThe silicon-carbon composite material can effectively relieve the volume expansion of a silicon material in the lithium ion de-intercalation process, simultaneously graphitizes a carbon material through carbonization treatment, and finally forms a silicon-carbon composite material after being compounded with the graphitized carbon material, so that the electronic conductivity of the silicon-carbon composite material is greatly improved, and the compatibility of the silicon-based material and an electrolyte is improved, so that the cycle performance and the rate capability of the material are improved, and the silicon-carbon composite material can be applied to a lithium ion battery cathode material with high power density and high energy density. Large volume change of silicon during lithium ion intercalation and deintercalation (>300%) causes electrode pulverization and electric contact between silicon and a current collector to be reduced, which leads to poor conductivity and reduced utilization rate of silicon, while the carbon material has higher electronic conductance, provides a better electronic channel for the composite material, and simultaneously can alleviate stress change caused by volume deformation of the silicon material after the carbon and the silicon material are compounded; in addition, carbon as a coating material can effectively stabilize the interface between an electrode material and electrolyte, so that an SEI film can stably grow, and the characteristics are beneficial to improving the electrochemical performance of the silicon negative electrode.
The porous silicon/carbon composite material is prepared by wet ball milling, high-temperature annealing (carbonization) and hydraulic ingot forming and adopting a low-temperature magnesiothermic reduction reaction. The silicon material and the carbon material are fully mixed and uniformly distributed by wet ball milling; then, carrying out carbonization treatment on the obtained product in a hydraulic ingot mode to graphitize the carbon material; the processed and uniformly mixed mixture of the glass powder and the carbon material is mixed with magnesium powder and molten salt, the mixture is pressed into ingots under the action of mechanical force, then magnesium thermal reaction is carried out under inert gas, silicate glass, the molten salt and the magnesium powder react in a liquid state, and a silicon-carbon composite material is formed in situ after acid cleaning.
According to the preparation method of the silicon-carbon composite material, silicate glass is used as a silicon source in the silicon-carbon composite material, and the silicate glass participating in magnesium thermal reaction can exist in a liquid state, so that the applicant of the invention creatively proposes that silicate glass powder and a carbon material are uniformly mixed and then are compacted into ingots before the magnesium thermal reaction, and then the magnesium thermal reaction is carried out, so that the density of the finally obtained silicon-carbon composite material is improved, and the energy volume density and the power energy density of the finally obtained silicon-carbon composite material are obviously improved when the silicon-carbon composite material is finally applied to a battery cathode material.
The steps of wet ball milling, high-temperature carbonization, hydraulic ingot formation, magnesium thermal reaction and final acid pickling cannot be changed in order, the wet ball milling ensures that the glass powder and the carbon material are uniformly mixed, and the uniform distribution of silicon and carbon in the finally prepared composite material can be ensured only by uniformly mixing and then performing subsequent carbonization, ingot pressing, reduction and acid pickling, so that good performances of the composite material are ensured; similarly, the carbonization step must be performed after the wet ball milling step and before the hydraulic ingot forming step, otherwise, the function of the carbonization step in preparing the target product silicon-carbon composite material cannot be realized, i.e., the silicon and the carbon are uniformly distributed in the final product, and good conductivity is obtained, the magnesium thermal reaction process has no impurity interference, no side reaction occurs, and the regular structure and good performance of the target product silicon-carbon composite material are further ensured, and the steps cooperate to form an independent and complete technical scheme together, so that the silicon-carbon composite material with high tap density and compacted density, good electronic conductivity, high specific mass capacity and volume capacity, limited electrode expansion and superior cycling stability is finally obtained.
The following are examples:
example 1
(1) Mixing 1-4 micron glass and asphalt according to a mass ratio of 10: 3, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 8 hours to obtain a mixture of glass and carbon-containing organic matters;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 500 ℃ at the heating rate of 2 ℃/min under the argon environment for heat preservation for 2h, and then is continuously heated to 800 ℃ at the heating rate of 5 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.5: 3, uniformly mixing, and then performing hydraulic pressing under the pressure of 4MPa to form ingots;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 680 ℃ at a heating rate of 5 ℃/min, and preserving heat for 4h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 1mol/L hydrochloric acid for 5 hours. And then cleaning the porous silicon/amorphous carbon composite material in 0.5mol/L hydrofluoric acid for 10 minutes, and pickling to obtain the porous silicon/amorphous carbon composite material.
As can be seen from the scanning electron microscope image in fig. 1, the silicon prepared in this embodiment belongs to silicon with a three-dimensional porous structure of a level of 1 to 5 micrometers, and is similar to a formicary shape, and the surface of the silicon is coated with a layer of amorphous carbon to form a coating structure.
As can be seen from the XRD diffraction pattern of figure 2, the three strong peaks at 28.4 deg., 47.3 deg. and 56.1 deg. correspond to the three strong peaks of silicon (JCPDS No.27-1402), the amorphous carbon peak position of steamed bread is obvious, and there is basically no impurity phase.
As can be seen from the transmission electron microscope image in fig. 3, the three-dimensional porous silicon prepared in this embodiment has an excellent pore structure, is integrally interconnected without damage, and has a pore diameter of 100 to 200 nm, and the thickness of the amorphous carbon coated on the surface of the porous silicon particles is 10 to 20 nm. The structure well relieves the volume expansion in the charging and discharging processes, increases the conductivity and can reveal the reason of excellent performance.
The porous silicon shown in FIG. 4 has excellent electrochemical cycling performance, the initial coulombic efficiency is as high as 89.9%, the capacity (1230mAh/g) is still higher after 300 cycles, the retention rate is as high as 83%, and the cycling stability is good, so that the porous silicon can be industrially produced and applied in a large scale.
As shown in FIG. 5, the amorphous carbon-coated porous silicon composite material had a specific surface area of 130m2g-1Wherein the pore diameter of the mesoporous is 2-6 nanometers. The tap density of the composite material is tested to be 1.16g/cm3The compacted density is 1.58g/cm3. The porous silicon synthesized by the method has a suitable specific surface area and an excellent pore structure,is suitable for the negative electrode material of the lithium battery.
From the thermogravimetric plot of fig. 6, the composite material had a silicon content of 85 wt% and a carbon content of 15 wt%.
Example 2
(1) Mixing 1-4 micron glass and asphalt according to a mass ratio of 10: 3, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 6 hours to obtain a mixture of glass and asphalt;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 550 ℃ at the heating rate of 2 ℃/min for heat preservation for 2h under the argon environment, and then is continuously heated to 850 ℃ at the heating rate of 7 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.5: 4, uniformly mixing, and then performing hydraulic pressing under the pressure of 3MPa to form ingots;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3h to obtain a reacted mixture;
(5) the reacted mixture obtained in step (4) was washed in 1.5mol/L hydrochloric acid for 3 hours. And then cleaning the porous silicon/amorphous carbon composite material in 0.2mol/L hydrofluoric acid for 30 minutes, and carrying out acid cleaning to obtain the porous silicon/amorphous carbon composite material.
Example 3
(1) Mixing 1-4 micron glass and coal tar according to a mass ratio of 10: 4, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically grinding for 10 hours to obtain a mixture of glass and coal tar;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 400 ℃ at the heating rate of 1 ℃/min under the argon environment for heat preservation for 3 hours, and then is continuously heated to 900 ℃ at the heating rate of 6 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.55: 3, uniformly mixing, and then hydraulically pressing into ingots under the pressure of 5 MPa;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 780 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6h to obtain a reacted mixture;
(5) the reacted mixture obtained in step (4) was washed in 2.5mol/L hydrochloric acid for 10 hours. And then cleaning the porous silicon/amorphous carbon composite material in 0.5mol/L hydrofluoric acid for 60 minutes, and carrying out acid cleaning to obtain the porous silicon/amorphous carbon composite material.
As can be seen from the scanning electron microscope image in fig. 7, the silicon prepared in this embodiment is a silicon with a three-dimensional porous structure of 1-5 μm level, and the surface of the silicon is coated with a layer of amorphous carbon to form a coating structure.
Example 4
(1) Mixing 1-4 micron glass and coal tar according to a mass ratio of 10: 5, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically grinding for 12 hours to obtain a mixture of glass and coal tar;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 550 ℃ at the heating rate of 1 ℃/min under the argon environment for heat preservation for 1h, and then is continuously heated to 1000 ℃ at the heating rate of 10 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.6: 4, uniformly mixing, and then performing hydraulic pressing under the pressure of 4.5MPa to form ingots;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 680 ℃ at a heating rate of 5 ℃/min, and preserving heat for 6h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 2mol/L hydrochloric acid for 1 hour. And then cleaning the porous silicon/amorphous carbon composite material in 0.4mol/L hydrofluoric acid for 15 minutes, and carrying out acid cleaning to obtain the porous silicon/amorphous carbon composite material.
Example 5
(1) 1-4 micron glass and petroleum coke are mixed according to the mass ratio of 10: 3, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 8 hours to obtain a mixture of glass and petroleum coke;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 500 ℃ at the heating rate of 5 ℃/min under the argon environment for heat preservation for 2h, and then is continuously heated to 900 ℃ at the heating rate of 5 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.6: 5, uniformly mixing, and then performing hydraulic pressing under the pressure of 3MPa to form ingots;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 2mol/L hydrochloric acid for 10 hours. And then cleaning the porous silicon/amorphous carbon composite material in 1mol/L hydrofluoric acid for 5 minutes, and carrying out acid cleaning to obtain the porous silicon/amorphous carbon composite material.
Example 6
(1) Mixing 1-4 micron glass and petroleum coke according to a mass ratio of 10: 4, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 12 hours to obtain a mixture of glass and petroleum coke;
(2) the mixture of the glass and the asphalt obtained in the step (1) is hydraulically pressed into ingots under the pressure of 1MPa, and then is heated to 550 ℃ at the heating rate of 3 ℃/min for heat preservation for 2h under the argon environment, and then is continuously heated to 850 ℃ at the heating rate of 10 ℃/min for carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.55: 5, uniformly mixing, and then hydraulically pressing into ingots under the pressure of 5 MPa;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 680 ℃ at a heating rate of 3 ℃/min, and preserving heat for 6h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 0.2mol/L hydrochloric acid for 5 hours. And then cleaning the porous silicon/amorphous carbon composite material in 0.5mol/L hydrofluoric acid for 30 minutes, and carrying out acid cleaning to obtain the porous silicon/amorphous carbon composite material.
Example 7
(1) Glass of 1-4 microns and carbon nanotubes are mixed according to a mass ratio of 10: 1, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 12 hours to obtain a mixture of glass and carbon nanotubes;
(2) the mixture of the glass and the carbon nano tube obtained in the step (1) is subjected to hydraulic pressure under the pressure of 1MPa to form an ingot, the ingot is heated to 550 ℃ at the heating rate of 3 ℃/min under the argon environment and is kept at the temperature for 2h, and then the ingot is continuously heated to 850 ℃ at the heating rate of 10 ℃/min to carry out carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.55: 5, uniformly mixing, and then hydraulically pressing into ingots under the pressure of 5 MPa;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 680 ℃ at a heating rate of 3 ℃/min, and preserving heat for 6h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 0.2mol/L hydrochloric acid for 5 hours. And then cleaning the silicon/carbon nanotube composite material in 0.5mol/L hydrofluoric acid for 30 minutes, and obtaining the porous silicon/carbon nanotube composite material after acid cleaning.
As can be seen from the scanning electron microscope image in FIG. 8, the carbon nanotubes and silicon are inlaid and interwoven into a network structure, the composite material comprises porous silicon and carbon nanotubes, wherein the carbon nanotubes are interwoven into a three-dimensional network structure, silicon is distributed in the spaces of the network structure, part of the carbon nanotubes are embedded into silicon particles, the particles are connected together and wrapped and interwoven to form a three-dimensional connected three-dimensional structure, the length of the carbon nanotubes is 10-20 micrometers, and the tap density of the composite material is 1.13-1.27 g/cm through measurement3The compaction density is 1.46-1.60 g/cm3A specific surface area of 105m2g-1。
Example 8
(1) Glass of 1-4 microns and bacterial cellulose are mixed according to the mass ratio of 10: 3, taking n-amyl alcohol as a ball grinding agent, putting the ball grinding agent into an agate tank, and mechanically ball-grinding for 12 hours to obtain a mixture of glass and bacterial cellulose;
(2) the mixture of the glass and the bacterial cellulose obtained in the step (1) is subjected to hydraulic pressure under the pressure of 1MPa to form ingots, then the ingots are heated to 550 ℃ at the heating rate of 3 ℃/min under the argon environment and are kept at the temperature for 2h, and then the ingots are continuously heated to 850 ℃ at the heating rate of 10 ℃/min to carry out carbonization treatment;
(3) grinding and grinding the sample obtained in the step (2), and mixing magnesium powder and molten salt according to a mass ratio of 1: 0.55: 5, uniformly mixing, and then hydraulically pressing into ingots under the pressure of 5 MPa;
(4) putting the sample ingot obtained in the step (3) into a tubular furnace filled with argon, heating to 680 ℃ at a heating rate of 3 ℃/min, and preserving heat for 6h to obtain a reacted mixture;
(5) and (3) washing the reacted mixture obtained in the step (4) in 0.2mol/L hydrochloric acid for 5 hours. And then cleaning the silicon/carbon nano fiber composite material in 0.5mol/L hydrofluoric acid for 30 minutes, and obtaining the porous silicon/carbon nano fiber composite material after acid cleaning.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the silicon-carbon composite material is characterized by comprising the following steps:
(1) mixing silicate glass powder and a carbon material, performing wet ball milling, performing solid-liquid separation, and drying to obtain a uniformly mixed mixture of the silicate glass powder and the carbon material;
(2) carbonizing the mixture of the silicate glass powder and the carbon material obtained in the step (1), and grinding the mixture after annealing to obtain a mixture of the silicate glass powder and the carbon material after carbonization; the carbonization treatment comprises the following specific steps: heating to 400-550 ℃ at a heating rate of 1-5 ℃/min under an argon environment, preserving heat for 1-3 h, then heating to 800-1000 ℃ at a heating rate of 5-10 ℃/min, and preserving heat for 2-4 h;
(3) mixing the mixture of the silicate glass powder and the carbon material subjected to carbonization treatment in the step (2), magnesium powder and molten salt, compacting into ingots, and then carrying out a magnesiothermic reduction reaction in an inert atmosphere; and carrying out acid washing treatment on the reaction product to obtain the silicon-carbon composite material.
2. The method according to claim 1, wherein the carbon material is a carbon-containing organic composite comprising one or more of pitch, petroleum coke, coal tar, phenol resin, graphene, and biomass carbon or a one-dimensional carbon material; the one-dimensional carbon material comprises one or more of carbon fiber, bacterial cellulose and carbon nanotubes.
3. The method according to claim 1, wherein the mass ratio of the silicate glass powder to the carbon material in the step (1) is 10:2 to 5.
4. The method according to claim 1, wherein before the carbonization treatment in the step (2), the method further comprises the substeps of: and compacting the mixture of the silicate glass powder and the carbon material into an ingot, wherein the pressure range adopted by the compacting into the ingot is 0.5-2 MPa.
5. The preparation method according to claim 1, wherein the mass ratio of the mixture of the silicate glass powder and the carbon material after the carbonization treatment in the step (3) to the magnesium powder and the molten salt is 1: 0.5-0.6: 3 to 5.
6. The method according to claim 1 or 4, wherein the pressure for compacting into an ingot in the step (3) is in the range of 1 to 5 MPa.
7. The method of claim 6, wherein the compacting into a billet is accomplished by a press or cold extruder.
8. The method according to claim 1, wherein the magnesiothermic reduction reaction conditions in step (3) are: heating to 600-800 ℃ at a heating rate of 2-5 ℃/min in an argon atmosphere, and preserving heat for 3-6 h.
9. A silicon-carbon composite material, characterized in that the silicon-carbon composite material is prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the silicon carbon composite material according to claim 9 as a negative electrode material for lithium ion batteries.
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| CN112331852B (en) * | 2020-10-23 | 2022-03-11 | 浙江锂宸新材料科技有限公司 | Nitrogen self-doped carbon-coated silicon monoxide negative electrode material and preparation method and application thereof |
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Application publication date: 20180112 Assignee: Hubei Benxing Carbon Material Co.,Ltd. Assignor: WUHAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2022420000139 Denomination of invention: A method, product and application for preparing silicon carbon composite material from silicate glass Granted publication date: 20200519 License type: Exclusive License Record date: 20221206 |